The invention relates to novel substituted, optically active aminotriazines having at least two asymmetrically substituted carbon atoms, to a process for their preparation and to their use as herbicides.
Substituted aminotriazines are already known from the (patent) literature (cf. U.S. Pat. No. 3,816,419, U.S. Pat. No. 3,932,167, EP-191 496, EP-273 328, EP-411 153/WO 90/09 378, WO 97/00 254, WO 97/08 156). However, these compoundsxe2x80x94some of which also have asymmetrically substituted carbon atomsxe2x80x94have hitherto not attained any particular importance.
This invention, accordingly, provides the novel substituted, optically active aminotriazines having at least two asymmetrically substituted carbon atoms of the general formula (I) 
in which
A represents a single bond or represents in each case straight-chain or branched alkanediyl or oxaalkanediyl having in each case up to 6 carbon atoms,
R1 represents amino, represents formylamino or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkylamino, dialkylamino, alkylcarbonylamino, N-alkyl-N-alkylcarbonylamino, alkoxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, alkylaminoalkylideneamino or dialkylaminoalkylideneamino having in each case up to 6 carbon atoms in the alkyl groups or alkylidene groups,
R2 represents hydrogen, halogen or optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having up to 6 carbon atoms,
R3 represents hydrogen, halogen or optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having up to 6 carbon atoms, or together with R2 represents optionally cyano-, halogen- or C1-C4-alkyl-substituted alkanediyl having 2 to 5 carbon atoms,
R4 represents alkyl having up to 6 carbon atoms or represents cycloalkyl having 3 to 6 carbon atoms,
Y represents hydrogen, hydroxyl, mercapto, amino, cyano, halogen, or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylthio, alkylamino or dialkylamino having in each case up to 6 carbon atoms in the alkyl groups, and
Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic group from the group consisting of cyclopentyl, cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, di-hydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl,
xe2x80x83where the possible substituents are in each case preferably selected from the group below:
hydroxyl, amino, cyano, nitro, carbamoyl, sulphamoyl, halogen, in each case optionally hydroxyl-, cyano- or halogen-substituted alkyl, alkoxy, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally halogen-substituted alkylcarbonyl, alkoxycarbonyl, alkylcarbonylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylsulphonylamino, alkylaminosulphonyl or dialkylaminosulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, in each case optionally hydroxyl-, cyano-, nitro-, halogen-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkoxy-substituted phenyl or phenoxy, and in each case optionally halogen-substituted methylenedioxy or ethylenedioxy,
xe2x80x83with the proviso that in each individual case R2, R3 and Y are different from one another and that the substituents at the two carbon atoms to which R2 and R3 or R4 are attached are configured as follows:
(a) R configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cR,R-diastereomersxe2x80x9d),
(b) R configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cR,S-diastereomersxe2x80x9d),
(c) S configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cS,R-diastereomersxe2x80x9d),
(d) S configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cS,S-diastereomersxe2x80x9d),
(e) R configuration at the carbon atom to which R2 and R3 are attached and racemic configuration at the carbon atom to which R4 is attached (xe2x80x9cR,rac-diastereomersxe2x80x9d),
(f) S configuration at the carbon atom to which R2 and R3 are attached and racemic configuration at the carbon atom to which R4 is attached (xe2x80x9cS,rac-diastereomersxe2x80x9d).
Since the C atom to which R2, R3 and Y are attached is not present in racemic form, all compounds according to the invention are optically active.
The novel substituted aminotriazines having at least two asymmetrically substituted carbon atoms of the general formula (I) are obtained when substituted biguanides of the general formula (II) 
in which
A, R1, R4 and Z are as defined above,
xe2x80x94and/or acid adducts of compounds of the general formula (II)xe2x80x94 are reacted with (optically active) carboxylic acid derivatives of the general formula (III) 
in which
R2, R3 and Y are as defined above and
X represents halogen or alkoxy,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
and, if appropriate, further conversions within the scope of the above definition of the substituents are carried out by customary methods on the resulting compounds of the general formula (I).
The compounds of the general formula (I) can be converted by customary methods into other compounds of the general formula (I) according to the above definition of the substituents, for example by acylation of compounds of the formula (I) in which R1 represents amino and/or Y represents hydroxyl, for example using acetyl chloride or propionyl chloride, or, for example, by fluorination of compounds of the formula (I) in which Y represents hydroxyl, for example using diethylaminosulphur tri-fluoride (xe2x80x9cDASTxe2x80x9d)xe2x80x94cf. the Preparation Examples.
The novel substituted aminotriazines having at least two asymmetrically substituted carbon atoms of the general formula (I) have strong and selective herbicidal activity. To a certain extent, they also have fungicidal and insecticidal activity.
In the definitions, the hydrocarbon chains, such as in alkyl, are in each case straight-chain or branchedxe2x80x94including in combination with heteroatoms, such as in alkoxy or alkylthio.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably represents fluorine, chlorine or bromine, in particular represents fluorine or chlorine.
The invention preferably provides compounds of the formula (I), in which
A represents a single bond, represents methylene (xe2x80x94CH2xe2x80x94), dimethylene (ethane-1,2-diyl, xe2x80x94CH2CH2xe2x80x94), ethylidene (ethane-1,1-diyl, xe2x80x94CH(CH3,)xe2x80x94), oxaethanediyl (xe2x80x94CH2Oxe2x80x94), trimethylene (propane-1,3-diyl, xe2x80x94CH2CH2CH2xe2x80x94), propylidene (propane-1,1-diyl, xe2x80x94CH(C2H5)xe2x80x94), propane-2,3-diyl (xe2x80x94CH(CH3)CH2xe2x80x94), 2-methylpropane-1,3-diyl (xe2x80x94CH2CH(CH3)CH2xe2x80x94), 3-oxapropane-1,3-diyl (xe2x80x94CH2CH2Oxe2x80x94), 2-oxapropane-1,3-diyl (xe2x80x94CH2OCH2xe2x80x94), tetramethylene (butane-1,4-diyl, xe2x80x94CH2CH2CH2CH2xe2x80x94), butane-2,4-diyl (xe2x80x94CH(CH3)CH2CH2xe2x80x94), butane-2,3-diyl (xe2x80x94CH(CH3)CH(CH3)xe2x80x94), 3-methylbutane-2,4-diyl (xe2x80x94CH(CH3)CH(CH3)CH2xe2x80x94), 4-oxabutane-2,4-diyl (xe2x80x94CH(CH3)CH2Oxe2x80x94), pentane-3,5-diyl (xe2x80x94CH(C2H5)CH2CH2xe2x80x94), 5-oxa-pentane-3,5-diyl (xe2x80x94CH(C2H5)CH2Oxe2x80x94), 4-oxapentane-2,5-diyl (xe2x80x94CH(CH3)CH2OCH2xe2x80x94) or 5-oxahexane-3,6-diyl (xe2x80x94CH(C2H5)CH2OCH2),
R1 represents amino, represents formylamino or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methylamino, ethylamino, dimethylamino, acetylamino, propionylamino, n- or i-butyroylamino, N-methyl-N-acetylamino, N-ethyl-N-acetylamino, N-methyl-N-propionylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, N-methyl-N-methoxycarbonylamino, N-ethyl-N-methoxycarbonylamino, N-methyl-N-ethoxycarbonylamino, methylaminomethyleneamino, ethylaminomethyleneamino, methylaminoethylideneamino or dimethylaminomethyleneamino,
R2 represents hydrogen, fluorine, chlorine, bromine, or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R3 represents hydrogen, fluorine, chlorine, bromine, or in each case optionally cyano-, fluorine-, chlorine, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or together with R2 represents in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted dimethylene (ethane-1,2-diyl), trimethylene (propane-1,3-diyl) or tetramethylene (butane-1,4-diyl),
R4 represents methyl, ethyl, n- or i-propyl, or represents cyclopropyl,
Y represents hydrogen, hydroxyl, mercapto, amino, cyano, fluorine, chlorine, bromine, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, acetyloxy, propionyloxy, n- or i-butyroyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, n- or i-propoxycarbonyloxy, methylaminocarbonyloxy, ethylaminocarbonyloxy, n- or i-propylaminocarbonyloxy, dimethylaminocarbonyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i- or s-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i- or s-butylamino or dimethylamino, and
Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the group consisting of cyclohexyl, phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, oxadiazolyl, thiadiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl,
xe2x80x83where the possible substituents are in each case preferably selected from the group below:
hydroxyl, amino, cyano, nitro, carbamoyl, sulphamoyl, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino or dimethylamino, in each case optionally fluorine- and/or chlorine-substituted acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, acetylamino, propionylamino, n- or i-butyroylaminio, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulphinyl, ethyl-sulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, methylsulphonylamino, ethylsulphonylamino, n- or i-propylsulphonylamino, methylaminosulphonyl, ethylaminosulphonyl, n- or i-propylaminosulphonyl, or dimethylaminosulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-, difluoromethoxy- or trifluoromethoxy-substiuted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy,
xe2x80x83with the proviso that in each individual case R2, R3 and Y are different from one another and that the substituents at the carbon atoms to which R2 and R3 or R4 are attached are configured as follows:
(a) R configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cR,R-diastereomersxe2x80x9d),
(b) R configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cR,S-diastereomersxe2x80x9d),
(c) S configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cS,R-diastereomersxe2x80x9d),
(d) S configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cS,S-diastereomersxe2x80x9d),
(e) R configuration at the carbon atom to which R2 and R3 are attached and racemic configuration at the carbon atom to which R4 is attached (xe2x80x9cR,rac-diastereomersxe2x80x9d),
(f) S configuration at the carbon atom to which R2 and R3 are attached and racemic configuration at the carbon atom to which R4 is attached (xe2x80x9cS,rac-diastereomersxe2x80x9d).
The invention relates in particular to compounds of the formula (I), in which
A represents a single bond, represents dimethylene (ethane-1,2-diyl, xe2x80x94CH2CH2xe2x80x94), oxaethanediyl (xe2x80x94CH2Oxe2x80x94) or 2-oxapropane-1,3-diyl (xe2x80x94CH2OCH2xe2x80x94),
R1 represents amino, represents formylamino or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino, or di-methylaminomethyleneamino,
R2 represents hydrogen, fluorine, chlorine, or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl,
R3 represents hydrogen, fluorine, chlorine, bromine, or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or together with R2 represents in each case optionally cyano-, fluorine-, chlorine- or methyl-substituted dimethylene (ethane-1,2-diyl),
R4 represents methyl or ethyl,
Y represents hydrogen, hydroxyl, cyano, fluorine, chlorine, bromine, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, acetyloxy, propionyloxy, methoxycarbonyloxy, ethoxycarbonyloxy, methylaminocarbonyloxy, ethylaminocarbonyloxy or dimethylaminocarbonyloxy, and
Z represents an optionally substituted monocyclic or bicyclic, carbocyclic or heterocyclic grouping from the group consisting of phenyl, naphthyl, tetralinyl, decalinyl, indanyl, indenyl, furyl, benzofuryl, dihydrobenzofuryl, thienyl, benzothienyl, dihydrobenzothienyl, isobenzofuryl, dihydroisobenzofuryl, isobenzothienyl, dihydroisobenzothienyl, pyrrolyl, indolyl, isoindolyl, indolinyl, isoindolinyl, benzodioxolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, benzimidazolyl, indazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolyl, isoquinolyl, quinoxalinyl, cinnolinyl and phthalazinyl,
xe2x80x83where the possible substituents are in each case preferably selected from the group below:
hydroxyl, amino, cyano, nitro, carbamoyl, sulphamoyl, fluorine, chlorine, bromine, in each case optionally hydroxyl-, cyano-, fluorine- or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, dimethylamino, in each case optionally fluorine- and/or chlorine-substituted acetyl, methoxycarbonyl, ethoxycarbonyl, dimethylaminocarbonyl, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl, ethylsulphonyl or dimethylaminosulphonyl, in each case optionally hydroxyl-, cyano-, nitro-, fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl or phenoxy, and in each case optionally fluorine- and/or chlorine-substituted methylenedioxy or ethylenedioxy,
xe2x80x83with the proviso that in each individual case R2, R3 and Y are different from one another and that the substituents at the carbon atoms to which R2 and R3 or R4 are attached are configured as follows:
(a) R configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cR,R-diastereomersxe2x80x9d),
(b) R configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cR,S-diastereomersxe2x80x9d),
(c) S configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cS,R-diastereomersxe2x80x9d),
(d) S configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cS,S-diastereomersxe2x80x9d).
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
Examples of the compounds of the general formula (I) according to the invention are listed in the groups below.
Group I 
Here, R1 represents, for example, amino, formylamino, acetylamino, propionylamino or dimethylaminomethyleneamino.
Here, the triazine substituent with R2, R3 and Y represents, for example, the groupings below:
xe2x80x94CH(CH3)C2H5, xe2x80x94CH(CH3)C3H7-n, xe2x80x94CH(CH3)C3H7-i, xe2x80x94CH(C2H5)C3H7-n, xe2x80x94CH(C2H5)C3H7-i, xe2x80x94C(CH3)(C2H5)C3H7-n, xe2x80x94C(CH3)(C2 H5)C3H7-i, xe2x80x94CH(OH)CH3, xe2x80x94CH(OH)C2H5, xe2x80x94CH(OH)C3H7-n, xe2x80x94CH(OH)C3H7-i, xe2x80x94CH(OCHO)CH3, xe2x80x94CH(OCHO)C2H5, xe2x80x94CH(OCHO)C3H7-n, xe2x80x94CH(OCHO)C3H7-i, xe2x80x94CH(OCOCH3)CH3, xe2x80x94CH(OCOCH3)C2H5, xe2x80x94CH(OCOCH3)C3H7-n, xe2x80x94CH(OCOCH3)C3H7-i, xe2x80x94CH(OCOC2H5)CH3, xe2x80x94CH(OCOC3H7-n)CH3, xe2x80x94CH(OCOC3H7-i)CH3, xe2x80x94C(OH)(CH3)C2H5, xe2x80x94C(OH)(CH3)C3H7-n, xe2x80x94C(OH)(CH3)C3H7-i, xe2x80x94CH(SH)CH3, xe2x80x94CHBrCH3, xe2x80x94CHBrC2H5, xe2x80x94CHBrC3H7-n, xe2x80x94CHBrC3H7-i, xe2x80x94CBrCH3)C2H5, xe2x80x94CBrCH3)C3H7-n, xe2x80x94CBr(CH3)C3H7-i, xe2x80x94CHClCH3, xe2x80x94CHClC2H5, xe2x80x94CHClC3H7-n, xe2x80x94CHClC3H7-i, xe2x80x94CCl(CH3)C2H5, xe2x80x94CCl(CH3)C3H7-n, xe2x80x94CCl(CH3)C3H7-i, xe2x80x94CHFCH3, xe2x80x94CHFC2H5, xe2x80x94CHFC3H7-n, xe2x80x94CHFC3H7-i, xe2x80x94CF(CH3)C2H5, xe2x80x94CF(CH3)C3H7-n, xe2x80x94CF(CH3)C3H7-i, xe2x80x94CH(CF3)CH3, xe2x80x94CH(CF3)C2H5, xe2x80x94CH(CF3)C3H7-n, xe2x80x94CH(CF3)C3H7-i, xe2x80x94C(CF3)(CH3)C2H5, xe2x80x94C(CF3)(CH3)C3H7-n, xe2x80x94C(CF3)(CH3)C3H7-i, xe2x80x94CH(OH)CF3, xe2x80x94C(OH)(CF3)CH3, xe2x80x94CF(OH)CF3, xe2x80x94CH(CH3)OCH3, xe2x80x94CH(C2H5)OCH3, xe2x80x94CH(C3H7-n)OCH3, xe2x80x94CH(C3H7-i)OCH3, xe2x80x94C(CH3)(C2H5)OCH3, xe2x80x94C(CH3)(C3H7-n)OCH3, xe2x80x94C(CH3)(C3H7-i)OCH3, xe2x80x94CH(CH3)OC2H5, xe2x80x94CH(C2H5)OC2H5, xe2x80x94CH(C3H7-n)OC2H5, xe2x80x94CH(C3H7-i)OC2H5, xe2x80x94CH(CH3)OC3H7-n, xe2x80x94CH(CH3)OC3H7-i, xe2x80x94CH(C2H5)OC3H7-n, xe2x80x94CH(C2H5)OC3H7-i, xe2x80x94CH(CF3)OCH3, xe2x80x94CH(CF3)OC2H5, xe2x80x94CHFCF3, xe2x80x94CHClCF3, xe2x80x94CF(CH3)CF3, xe2x80x94CF(C2H5)CF3, xe2x80x94CF(C3H7-n)CF3, xe2x80x94CF(C3H7-i)CF3, xe2x80x94CH(CN)CH3, xe2x80x94CH(CN)C2H5, xe2x80x94CH(CN)C3H7-n, xe2x80x94CH(CN)C3H7-i, xe2x80x94C(CN)(CH3)C2H5, xe2x80x94C(CN)(CH3)C3H7-n, xe2x80x94C(CN)(CH3)C3H7-n, xe2x80x94CH(CH3)SCH3, xe2x80x94CH(C2H5)SCH3, xe2x80x94CH(C3H7-n)SCH3, xe2x80x94CH(C3H7-i)SCH3, xe2x80x94C(CH3)(C2H5)SCH3, xe2x80x94C(CH3)(C3H7-n)SCH3, xe2x80x94C(CH3)(C3H7-i)SCH3, xe2x80x94CH(CH3)SC2H5, xe2x80x94CH(C2H5)SC2H5, xe2x80x94CH(C3H7-n)SC2H5, xe2x80x94CH(C3H7-i)SC2H5, xe2x80x94CHFBr,xe2x80x94CHFCl, xe2x80x94CFBrCH3, xe2x80x94CFClCH3, xe2x80x94CFBrCl, xe2x80x94CH(CH2Cl)Cl, xe2x80x94CH(CH3)CH2OCH3, xe2x80x94CH(CH3)CH2OC2H5, xe2x80x94CH(C2H5)CH2OCH3, xe2x80x94CH(CH3)CH2CH2OCH3, 
For each of the examples listed here and in the groups below by formulae and radical definitions, particular emphasis is given to the diastereomeric forms described below:
(a) R configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cR,R-diastereomersxe2x80x9d),
(b) R configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cR,S-diastereomersxe2x80x9d),
(c) S configuration at the carbon atom to which R2 and R3 are attached and R configuration at the carbon atom to which R4 is attached (xe2x80x9cS,R-diastereomersxe2x80x9d),
(d) S configuration at the carbon atom to which R2 and R3 are attached and S configuration at the carbon atom to which R4 is attached (xe2x80x9cS,S-diastereomersxe2x80x9d).
Group 2
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 3
Here, R1, R2, R3 and Y have, for example, the meanings given above in group I.
Group 4
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 5
Here, R1, R2, R3 and Y have, for example, the meanings (given above in group 1.
Group 6
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 7
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 8
Here, R1 R2, R3 and Y have, for example, the meanings given above in group 1.
Group 9
Here, R1, R2, R and Y have, for example, the meanings given above in group 1.
Group 10
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 11
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 12
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 13
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 13a 
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 14
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 15
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 16
Here R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 17
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 18
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 19
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 20
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 21
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 22
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 23
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 24
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 25
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 26
Here R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 27
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 28
Here R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 29
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 30
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 31
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 32
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 33
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 34
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 35
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 36
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 37
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 38
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 39
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 40
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 41
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 42
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 43
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 44
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 45
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 46
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 47
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 48
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 49
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Group 50
Here, R1, R2, R3 and Y have, for example, the meanings given above in group 1.
Using, for example, (S)-1-(1-phenylpropyl)biguanide and ethyl (S)-1-chloropropionate as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme: 
The formula (II) provides a general definition of the substituted biguanides to be used as starting materials in the process according to the invention for preparing compounds of the formula (I). In the formula (II), A, R1, R4 and Z each preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for A, R1, R4 and Z.
The starting materials of the general formula (II) are known and/or can be prepared by processes known per se (cf. EP-509 544, U.S. Pat. No. 3,816,419, U.S. Pat. No. 3,860,648, WO 97/00 254, WO 97/08 156, DE-19 641 691 (Le A 31 995), DE-19 641 692 (Le A 32 037), DE-19 641 693 (Le A 31 975), Preparation Examples).
The formula (III) provides a general definition of the carboxylic acid derivatives further to be used as starting materials in the process according to the invention. In the formula (III), R2, R3 and Y each preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for R2, R3 and Y; X preferably represents fluorine, chlorine, bromine or C1-C4-alkoxy, in particular represents methoxy or ethoxy.
The starting materials of the general formula (III) are known and/or can be prepared by processes known per se (cf. J. Chem. Soc. Perkin Trans. I, 1979, 2248-2252; Preparation Examples).
The process according to the invention for preparing the compounds of the general formula (I) is preferably carried out using a reaction auxiliary. Suitable reaction auxiliaries for the process according to the invention are, in general, the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diaza-bicyclo[2,2,2]octane (DABCO), 1,5-diazabicyclo[4,3,0]non-5-ene (DBN), or 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).
The process according to the invention for preparing the compounds of the general formula (I) is preferably carried out using a diluent. Suitable diluents for carrying out the process according to the invention are especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl sulphoxide; alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 10xc2x0 C. and 100xc2x0 C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use a relatively large excess of one of the components. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the required temperature. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed killers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlomitrofen, chlorsulfuron, chlorotoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-P-butyl), flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachltor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop(-P-ethyl), quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering.
The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.